Catalyst Structure and Method of Fischer-Tropsch Synthesis

ABSTRACT

The present invention includes Fischer-Tropsch catalysts, reactions using Fischer-Tropsch catalysts, methods of making Fischer-Tropsch catalysts, processes of hydrogenating carbon monoxide, and fuels made using these processes. The invention provides the ability to hydrogenate carbon monoxide with low contact times, good conversion rates and low methane selectivities. In a preferred method, the catalyst is made using a metal foam support.

RELATED APPLICATIONS

This application is a continuation of U.S. Ser. No. 11/231,708, filedSep. 20, 2005, now U.S. Pat. No. ______ which was a divisional of U.S.Ser. No. 10/392,479, now U.S. Pat. No. 6,982,287 which was a divisionalof U.S. Ser. No. 09/492,254 filed Jan. 27, 2000, now U.S. Pat. No.6,558,634, which was a continuation-in-part of U.S. Ser. No. 09/375,610,filed Aug. 17, 1999, now U.S. Pat. No. 6,451,864, all of which areincorporated by reference.

FIELD OF THE INVENTION

The present invention is a catalyst structure and method of making, anda method of Fischer-Tropsch synthesis.

BACKGROUND OF THE INVENTION

Fischer-Tropsch synthesis is carbon monoxide hydrogenation that isusually performed on a product stream from another reaction includingbut not limited to steam reforming (product stream H₂/CO˜3), partialoxidation (product stream H₂/CO˜2), autothermal reforming (productstream H₂/CO˜2.5), CO₂ reforming (H₂/CO˜1) coal gassification (productstream H₂/CO˜1) and combinations thereof.

Fundamentally, Fischer-Tropsch synthesis has fast surface reactionkinetics. However, the overall reaction rate is severely limited by heatand mass transfer with conventional catalysts or catalyst structures.The limited heat transfer together with the fast surface reactionkinetics may result in hot spots in a catalyst bed. Hot spots favormethanation. In commercial processes, fixed bed reactors with smallinternal diameters or slurry type and fluidized type reactors with smallcatalyst particles (>50 microns, μm) are used to mitigate the heat andmass transfer limitations. In addition, one of the important reasonsthat Fischer-Tropsch reactors are operated at lower conversions per passis to minimize temperature excursion in the catalyst bed. Because of thenecessary operational parameters to avoid methanation, conventionalreactors are not improved even with more active Fischer-Tropschsynthesis catalysts. Detailed operation is summarized in Table 1 andFIG. 1.

TABLE 1 Comparison of Contact Times Effects in Fischer-TropschExperimentation Contact CH₄ Ref^((A)) Catalyst Conditions timeConversion selectivity 1 Co/ZSM-5 240° C., 20-atm, H₂/CO = 2 3.6-sec 60%21% 2 Co/MnO 220° C., 21-atm, H₂/CO = 2 0.72-sec  13% 15% 3 Co—Ru/TiO₂200° C., 20-atm, H₂/CO = 2   3-sec 61%  5% Co/TiO₂ ″   8-sec 49%  7% 4Co/TiO₂ 200° C., 20-atm, H₂/CO = 2.1   2-sec 9.5%  ~9% ″  12-sec 72% ~6%5 Ru/Al₂O₃ 222° C., 21-atm, H₂/CO = 3 4.5-sec 20% ? ″ 7.2-sec 36% ″8.4-sec 45% ″ 9.6-sec 51% ″  12-sec 68% ″  14-sec 84% 6 Ru/Al₂O₃ 250°C., 22-atm, H₂/CO = 2 7.2-sec 38%  5% 7 Ru/Al₂O₃ 225° C., 21-atm, H₂/CO= 2  12-sec 66% 13% 222° C., 21-atm, H₂/CO = 3  12-sec 77% 34% Forreferences that contained results for multiple experimental conditions,the run which best matched our conversion, selectivity and/or conditionswas chosen for comparison of contact time. ^((A))References 1. Bessell,S., Appl. Catal. A: Gen. 96, 253 (1993). 2. Hutchings, G. J., TopicsCatal. 2, 163 (1995). 3. Iglesia, E., S. L. Soled and R. A. Fiato (ExxonRes. and Eng. Co.), U.S. Pat. No. 4,738,948, Apr. 19, 1988. 4. Iglesia,E., S. C. Reyes, R. J. Madon and S. L. Soled, Adv. Catal. 39, 221(1993). 5. Karn, F. S., J. F. Shultz and R. B. Anderson, Ind. Eng. Chem.Prod. Res. Dev. 4(4), 265 (1965). 6. King, F., E. Shutt and A. I.Thomson, Platinum Metals Rev. 29(44), 146 (1985). 7. Shultz, J. F., F.S. Karn and R. B. Anderson, Rep. Invest. - U.S. Bur. Mines 6974, 20(1967).

Literature data (Table 1 and FIG. 1) were obtained at lower H₂/CO ratio(2:1) and longer contact time (3 sec or longer) in a fixed bed typereactor. Low H₂/CO (especially 2-2.5), long contact time, lowtemperature, and higher pressure favor Fischer-Tropsch synthesis.Selectivity to CH₄ is significantly increased by increasing H₂/CO ratiofrom 2 to 3. Increasing contact time also has a dramatic favorableeffect on the catalyst performance. Although reference 3 in Table 1shows satisfactory results, the experiment was conducted under theconditions where Fischer-Tropsch synthesis is favored (at least 3 secresidence time, and H₂/CO=2). In addition, the experiment of reference 3was done using to a powdered catalyst on an experimental scale thatwould be impractical commercially because of the pressure drop penaltyimposed by powdered catalyst. Operating at higher temperature willenhance the conversion, however at the much higher expense ofselectivity to CH₄. It is also noteworthy that contact time incommercial Fischer-Tropsch units is at least 10 sec.

Hence, there is a need for a catalyst structure and method ofFischer-Tropsch synthesis that can achieve the same or higher conversionat shorter contact time, and/or at higher H₂/CO.

SUMMARY OF THE INVENTION

The present invention includes a catalyst structure and method of makingthe catalyst structure for Fischer-Tropsch synthesis that have a firstporous structure with a first pore surface area and a first pore size ofat least about 0.1 μm, preferably from about 10 μm to about 300 μm. Aporous interfacial layer with a second pore surface area and a secondpore size less than the first pore size disposed on the first poresurface area. A Fischer-Tropsch catalyst selected from the groupconsisting of cobalt, ruthenium, iron, nickel, rhenium, osmium andcombinations thereof is placed upon the second pore surface area.

The present invention also provides a method of making a Fischer-Tropschcatalyst having the steps of: providing a catalyst structure comprisinga porous support with a first pore surface area and a first pore size ofat least about 0.1 μm; optionally depositing a buffer layer on theporous support; depositing a porous interfacial layer with a second poresurface area and a second pore size less than said first pore size, uponthe buffer layer (if present); and depositing a Fischer-Tropsch catalystupon the second pore surface area.

The present invention further includes a method of Fischer-Tropschsynthesis having the steps of:

providing a catalyst structure having a first porous support with afirst pore surface area and a first pore size of at least about 0.1 μm;

a buffer layer disposed on the porous support;

a porous interfacial layer with a second pore surface area and a secondpore size less than the first pore size, the porous interfacial layerdisposed on the buffer layer (if present) or on the first pore surfacearea; and a Fischer-Tropsch catalyst disposed on the second pore surfacearea; and

(b) passing a feed stream having a mixture of hydrogen gas and carbonmonoxide gas through the catalyst structure and heating the catalyststructure to at least 200° C. at an operating pressure, the feed streamhaving a residence time within the catalyst structure less than 5seconds, thereby obtaining a product stream of at least 25% conversionof carbon monoxide, and at most 25% selectivity toward methane.

The present invention also includes various supported Fischer-Tropshcatalysts that are characterized by their properties. For example, acatalyst is provided that, if exposed to a feed stream consisting of a 3to 1 ratio of hydrogen gas to carbon monoxide, at 250° C. and aresidence time of 12.5 seconds, exhibits a selectivity to methane thatis greater at 24 atmospheres (contact time of 1 second) than it is at 6atmospheres pressure (contact time of 4 seconds), even though theconversion is higher at lower pressure.

Catalytic activity is an intrinsic property of a catalyst. In thepresent invention, this property is defined by various testingconditions. For example, a preferred catalyst has a Fischer-Tropschcatalytic metal supported on a porous support; where the catalystpossesses catalytic activity such that, if the catalyst is placed in atube inside an isothermal furnace and exposed to a feed streamconsisting of a 3 to 1 ratio of hydrogen gas to carbon monoxide, at 250°C., at 6 atm, at a contact time less than 5 seconds and the productstream is collected and cooled to room temperature, the selectivity tomethane is less than 25%, and the carbon monoxide conversion is greaterthan 25%. To check whether a catalyst meets a claimed activity propertyrequires only a test at the specified conditions.

The invention also provides a method for hydrogenating carbon monoxide,in which a feed stream containing hydrogen and carbon monoxide is passedinto a reaction chamber that contains a catalyst at a temperature of atleast 200° C.; the catalyst having a supported Fischer-Tropsch catalyticmetal; and collecting a product stream. In this process, heat istransferred from the reaction chamber at a sufficient rate such that,under steady-state conditions, the feed stream has: a contact time ofless than about 2 seconds; a production rate of at least 1 milliliterper minute of liquid product where the liquid product is measured at 20°C. and 1 atm or at least 1 liter per minute of gaseous hydrocarbonproduct of molecules having at least 2 carbon atoms; a methaneselectivity of less than 25%, and a carbon monoxide conversion greaterthan 25%. The hydrocarbons can be saturated, unsaturated or partiallyoxidized; and for use as fuels are preferably saturated hydrocarbons.

The present invention further includes reactors that use any of thecatalysts described herein. The invention also includes hydrocarbonfuels made by any of the methods described herein. The present inventionfurther includes methods of hydrogenating carbon monoxide that use anyof the catalysts described herein.

Advantages that may be provided by the invention include (i) atresidence/contact times shorter than the prior art, higher conversionsare achieved with no increase to methane selectivity; and (ii) asresidence/contact times increase, conversion increases and methaneselectivity decreases. Surprisingly, it has been found that carbonmonoxide can be hydrogenated at short contact time to produce liquidfuels at good conversion levels, low methane selectivities and goodproduction rates.

The subject matter of the present invention is particularly pointed outand distinctly claimed in the concluding portion of this specification.However, both the organization and method of operation, together withfurther advantages and objects thereof, may best be understood byreference to the following description taken in connection withaccompanying drawings wherein like reference characters refer to likeelements.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of CO conversion versus contact time for prior artFischer-Tropsch processes.

FIG. 2 is a cross section of a catalyst structure according to thepresent invention.

FIG. 3 illustrates a reactor design having multiple reaction chambers,each containing a catalyst, and multiple heat exchangers.

DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

A catalyst of the present invention is depicted in FIG. 1 having aporous support 100, a buffer layer 102, an interfacial layer 104, and,optionally, a catalyst layer 106. Any layer may be continuous ordiscontinuous as in the form of spots or dots, or in the form of a layerwith gaps or holes.

The porous support 100 may be a porous ceramic or a porous metal. Poroussupports suitable for use in the present invention include carbides,nitrides, and composite materials. Prior to depositing the layers, theporous support preferably has a porosity of about 30% to about 99%, morepreferably 60% to 98%, as measured by mercury porosimetry and an averagepore size of from 1 μm to 1000 μm as measured by optical and scanningelectron microscopy. Preferred forms of porous supports are foams,felts, wads and combinations thereof. Foam is a structure withcontinuous walls defining pores throughout the structure. Felt is astructure of fibers with interstitial spaces therebetween. Wad is astructure of tangled strands, like steel wool. Less preferably, poroussupports may also include other porous media such as pellets andhoneycombs, provided that they have the aforementioned porosity and poresize characteristics. The open cells of a metal foam preferably rangefrom about 20 pores per inch (ppi) to about 3000 ppi and more preferablyabout 40 to about 600 ppi. PPI is defined as the largest number of poresper inch (in isotropic materials the direction of the measurement isirrelevant; however, in anisotropic materials, the measurement is donein the direction that maximizes pore number). In the present invention,ppi is measured by scanning electron microscopy. It has been discoveredthat a porous support provides several advantages in the presentinvention including low pressure drop, enhanced thermal conductivityover conventional ceramic pellet supports, and ease of loading/unloadingin chemical reactors.

The buffer layer 102, if present, has different composition and/ordensity than both the support and the interfacial layers, and preferablyhas a coefficient of thermal expansion that is intermediate to thethermal expansion coefficients of the porous support and the interfaciallayer. Preferably, the buffer layer is a metal oxide or metal carbide.Applicants discovered that vapor-deposited layers are superior becausethey exhibit better adhesion and resist flaking even after severalthermal cycles. More preferably, the buffer layer is Al₂O₃, TiO₂, SiO₂,and ZrO₂ or combinations thereof. More specifically, the Al₂O₃ isα-Al₂O₃, γ-Al₂O₃ and combinations thereof. α-Al₂O₃ is more preferredbecause of its excellent resistance to oxygen diffusion. Therefore, itis expected that resistance against high temperature oxidation can beimproved with alumina coated on the porous support 100. The buffer layermay also be formed of two or more compositionally different sublayers.When the porous support 100 is metal, for example a stainless steelfoam, a preferred embodiment has a buffer layer 102 formed of twocompositionally different sub-layers (not shown). The first sublayer (incontact with the porous support 100) is preferably TiO₂ because itexhibits good adhesion to the porous metal support 100. The secondsublayer is preferably α-Al₂O₃ which is placed upon the TiO₂. In apreferred embodiment, the α-Al₂O₃ sublayer is a dense layer thatprovides excellent protection of the underlying metal surface. A lessdense, high surface area alumina interfacial layer may then be depositedas support for a catalytically active layer.

Typically the porous support 100 has a thermal coefficient of expansiondifferent from that of the interfacial layer 104. Accordingly, for hightemperature catalysis (T>150° C.) a buffer layer 102 can be used totransition between two coefficients of thermal expansion. The thermalexpansion coefficient of the buffer layer can be tailored by controllingthe composition to obtain an expansion coefficient that is compatiblewith the expansion coefficients of the porous support and interfaciallayers. Another advantage of the buffer layer 102 is that it providesresistance against side reactions such as coking or cracking caused by abare metal foam surface. For chemical reactions which do not requirelarge surface area supports such as catalytic combustion, the bufferlayer 102 stabilizes the catalyst metal due to strong metal tometal-oxide interaction. In chemical reactions which require largesurface area supports, the buffer layer 102 provides stronger bonding tothe high surface area interfacial layer 104. Preferably, the bufferlayer is free of openings and pin holes—this provides superiorprotection of the underlying support. More preferably, the buffer layeris nonporous. The buffer layer has a thickness that is less than onehalf of the average pore size of the porous support. Preferably, thebuffer layer is between about 0.05 and about 10 μm thick, morepreferably, less than 5 μm thick. The buffer layer should exhibitthermal and chemical stability at elevated temperatures.

In some embodiments of the present invention, adequate adhesion andchemical stability can be obtained without a buffer layer, so the bufferlayer can be omitted, thus saving cost, providing extra volume andfurther enhancing heat transfer from the catalyst.

The interfacial layer 104 can be comprised of nitrides, carbides,sulfides, halides, metal oxides, carbon and combinations thereof. Theinterfacial layer provides high surface area and/or provides a desirablecatalyst-support interaction for supported catalysts. The interfaciallayer can be comprised of any material that is conventionally used as acatalyst support. Preferably, the interfacial layer is a metal oxide.Examples of metal oxides include, but are not limited, to γ-Al₂O₃, SiO₂,ZrO₂, TiO₂, tungsten oxide, magnesium oxide, vanadium oxide, chromiumoxide, manganese oxide, iron oxide, nickel oxide, cobalt oxide, copperoxide, zinc oxide, molybdenum oxide, tin oxide, calcium oxide, aluminumoxide, lanthanum series oxide(s), zeolite(s) and combinations thereof.The interfacial layer 104 may serve as a catalytically active layerwithout any further catalytically active material deposited thereon.Usually, however, the interfacial layer 104 is used in combination withcatalytically active layer 106. The interfacial layer may also be formedof two or more compositionally different sublayers. The interfaciallayer has a thickness that is less than one half of the average poresize of the porous support. Preferably, the interfacial layer thicknessranges from about 0.5 to about 100 μm, more preferably from about 1 toabout 50 μm. The interfacial layer can be either crystalline oramorphous and preferably has a BET surface area of at least 1 m²/g.

The catalytically active material 106 (when present) can be deposited onthe interfacial layer 104. Alternatively, a catalytically activematerial can be simultaneously deposited with the interfacial layer. Thecatalytically active layer (when present) is typically intimatelydispersed on the interfacial layer. That the catalytically active layeris “disposed on” or “deposited on” the interfacial layer includes theconventional understanding that microscopic catalytically activeparticles are dispersed: on the support layer (i.e., interfacial layer)surface, in crevices in the support layer, and in open pores in thesupport layer. The present invention employs a Fischer-Tropsch catalyticmetal in the catalytically active layer. Conventional Fischer-Tropschcatalysts are based on iron (Fe), cobalt (Co), nickel (Ni), ruthenium(Ru), rhenium (Re), osmium (Os) and combinations thereof. Catalyticmetals in the present invention are preferably iron, cobalt, ruthenium,rhenium, osmium and combinations thereof. In addition to these catalystmetals, a promoter may be added. Promoters could include transitionmetals and metal oxides (except Au and Hg), lanthanide metals or metaloxides, and group IA elements (except H). A Fischer-Tropsch catalyticmetal combined with a suitable support such as the porous support withinterfacial layer described herein is termed a supported Fischer-Tropschcatalytic metal. In less preferred embodiments, the supportedFischer-Tropsch catalytic metal can be a Fischer-Tropsch catalytic metalsupported on other supports such as a powder.

In order to mitigate the mass transfer limitation of the catalyststructure, the catalyst impregnation preferably forms a porousinterfacial layer having a depth less than 50 μm, preferably less than20 μm. Therefore, the diffusion path length is at least a factor of 5shorter than for standard catalyst particles. The thinner impregnatedcatalyst structure also enhances heat transfer, due to a shorter heattransfer pathway, and leads to lower selectivity to CH₄.

The catalyst structure may be any geometric configuration. Preferably,the catalyst is a porous structure such as a foam, felt, wad andcombinations thereof. The catalyst (including the support andFischer-Tropsch catalytic metal). preferably is sized to fit within areaction chamber. The catalyst may be a single piece of porouscontiguous material, or many pieces in physical contact. The catalyst ispreferred to have contiguous material and contiguous porosity such thatmolecules can diffuse through the catalyst. In this preferredembodiment, the catalyst can be disposed in a reaction chamber such thatgases will flow substantially through the catalyst (single or multiplepieces) rather than around it. In a preferred embodiment, thecross-sectional area of the catalyst occupies at least 80%, morepreferably at least 95% of the cross-sectional area of the reactionchamber. In preferred embodiments, the catalytically active metal isdistributed on surfaces throughout catalyst such that reactants passingthrough the catalyst can react anywhere along the passage through thecatalyst; this is a significant advantage over pellet-type catalyststhat have a large volume of unused space or catalytically ineffectivelyused space in the pellet's interior. The porous catalyst is alsosuperior over powders because packed powders may cause a severe pressuredrop. The catalyst preferably has a surface area, as measured by BET, ofgreater than about 0.5 m²/g, more preferably greater than about 2.0m²/g.

In addition, because the catalyst structure is not required to beattrition resistant as would be with the catalyst particles used in afluidized bed reactor, greater porosity may be used, for exampleporosity greater than about 30%, thus, enhancing mass transfer in thecatalyst structure.

Catalysts of the present invention can also be characterized by theproperties they exhibit. Factors that can be controlled to effect theseproperties include: selection of the porous support, buffer,interfacial, and catalytically active layers; gradation of thermalexpansion coefficients, crystallinity, metal-support interactions,catalyst size, thermal conductivity of the support, porosity, thermalconductance from reaction chamber, deposition techniques and otherfactors as are apparent in view of the descriptions herein. Certainpreferred embodiments of the catalysts of the present invention exhibitone or more of the following properties: adhesion—after 3 thermal cyclesin air, the catalyst exhibits less than 2% (by area) of flaking asviewed by SEM (scanning electron microscope) analysis; oxidationresistance, conversion of carbon monoxide, contact times, methaneselectivity, pressure drop and production rates.

Oxidation resistance can be measured by thermal gravity analysis (TGA).After heating at 580° C. in air for 2500 minutes, the catalyst increasesin weight by less than 5%, more preferably less than 3%; still morepreferably, after heating at 750° C. in air for 1500 minutes, thecatalyst increases in weight by less than 0.5%. Each thermal cycleconsists of heating from room temperature to 600° C. in air at a heatingrate of 10° C./min, maintaining the temperature at 600° C. for 3000minutes, and cooling at a rate of 10° C./min.

Another aspect of the present invention is a catalyst and methodutilizing the catalyst that provides lower methane selectivity at lowerpressures. It was unexpectedly discovered that by using the porouscatalyst structure of the present invention, reducing the pressure ofthe Fischer-Tropsch reaction resulted in increased yield, lessselectivity toward methane. See Example 2.

Enhanced heat transfer in the present invention enables short contacttimes, good conversion, and low methane selectivities. Various factorsthat can be used to enhance heat transfer include: use of a metalsupport, preferably a porous metal support such as a metal foam or wad,thin buffer (if present) and interfacial layers, a heat exchanger inthermal contact with the reaction chamber, microchannels in reactionchamber and/or heat exchanger, and a catalyst that has a thickness inthe direction of heat transfer (e.g., the direction to the reactionchamber walls and substantially perpendicular to the direction of flow)of about 1.5 cm or less, more preferably about 1 to 10 mm, and stillmore preferably about 1 to 3 mm.

The invention further provides apparatusses (i.e., reactors) and methodsfor hydrogenating carbon monoxide. In a preferred embodiment, thecatalytic process is conducted in apparatus having microchannels. Amicrochannel has a characteristic dimension less than about 1 mm. In oneembodiment, the reaction chamber has walls defining at least onemicrochannel through which pass reactants into the reaction chamber. Ina preferred embodiment, the reaction chamber walls separate the reactionchamber from at least one cooling chamber. Examples of suitablemicrochannel apparatus and various process related factors are describedin U.S. Pat. Nos. 5,611,214, 5,811,062, 5,534,328, 6,129,973, 6,192,596,6,200,536, 6,488,838 and 6,540,975 all of which are incorporated byreference as if reproduced in full below. In another preferredembodiment, the catalyst is a monolith—a single contiguous, yet porous,piece of catalyst or several contiguous pieces that are stacked together(not a bed of packed powder or pellets or a coating on the wall of amicrochannel) that can easily be inserted and extracted from a reactionchamber. The piece or stack of catalyst pieces preferably have a widthof 0.1 mm to about 2 cm, with a preferred thickness of less than about1.5 cm, more preferably less than about 1.0 cm, and still morepreferably, about 1 to about 3 mm. The inventive catalyst may providenumerous advantages to catalytic processes such as: chemical stability,stability to repeated thermal cycling, thermal stability, efficientloading and unloading of catalysts, high rates of heat transfer and masstransfer, and maintenance of desired catalytic activity.

The metal surfaces within microchannel apparatus can be coated witheither or both the buffer and the interfacial layers. This can be doneusing any of the processes described herein, preferably by vapordeposition. Preferred coating materials include titania and 5-10%SiO₂/Al₂O₃. The interior surfaces of the reaction chamber, heatexchanger and other surfaces of microchannel apparatus may be coated. Insome embodiments, the walls of a reaction chamber can be coated with anoptional buffer layer, an interfacial layer, and a catalytically activematerial—typically the catalytically active material and the interfaciallayer combine to form a supported catalyst. Coatings can also be appliedto metal walls in tubes and pipes that form connections to or withinmicrochannel apparatus.

According a preferred method of the present invention, residence timeless than 5 seconds can be achieved by: (a) providing a catalyststructure of a metal foam having a catalyst thereon; and (b) passing afeed stream having a mixture of hydrogen gas with carbon monoxide gasthrough the catalyst structure and heating the catalyst structure to atleast 200° C., thereby obtaining a product stream of at least 25%conversion of carbon monoxide, and at most 25% selectivity towardmethane. In another preferred method, the catalyst structure includes abuffer layer and an interfacial layer with a catalytically active metaldisposed on the interfacial layer.

The present invention provides processes for hydrogenating carbonmonoxide. In preferred processes, the ratio of hydrogen to carbonmonoxide ranges from about 1:1 to about 6:1, preferably from about 2:1to about 3.5:1. Hydrogenation is preferably conducted at temperaturesabove about 200° C., more preferably between about 200° C. and about300° C., and still more preferably between about 200° C. and about 270°C.

Certain embodiments of the present invention can be characterized interms of residence or contact time. These terms have well-definedmeanings in the art. Contact time is the total volume of the catalystchambers divided by the to total flowrate of inlet reactants assumingthey are an ideal gas corrected to standard conditions (i.e., the volumeof the catalyst chamber/F-total at STP where STP is 273K and 1 atm). Thevolume of the catalyst chambers includes the volume in immediateproximity and surrounding the catalyst zone. As an example, if one wereto pack one quarter of the channels with powders, then the volume of thecatalyst chamber would only include that region where gas can flow andwhere it can contact the catalyst, i.e. only one quarter of the totalchannel volume would be included in this calculation. The volume of deadspace, i.e., headers, footers, etc. is ignored in this calculation.Average residence time (also referred to as residence time) is the totalvolume of the catalyst chambers divided by the total flowrate of inletreactants, corrected to the actual temperature and pressure of thereactants in the reactor (i.e., the volume of the catalystchamber/F-total corrected to actual conditions). F-total at STP is thetotal volumetric flowrate of reactants (includes all reactants, anddiluents if present). Inlet gases are typically metered with mass flowcontrollers set to standard conditions, i.e. the user presets thedesired STP flowrate. F-total corrected to actualconditions=F-total-STP×(Temperature in K)/273×1 atm/(P actual in atm):this value is used to calculate the residence time or the ‘true time’within a reactor. Most practitioners prefer to use contact time, becauseit is a convenient method to keep the time variable fixed while steppingthrough 10 degree C. increments in reaction temperature etc.

Contact times less than 5 seconds may be accomplished with standardequipment but at the expense of significant energy to raise the spacevelocity of the reactants to overcome the pressure drop and poorer heattransfer leading to higher methane formation. Thus, the inventive methodis preferably carried out in a reaction chamber in which the catalysthas a thickness of about 1.5 cm or less and is touching or in closeproximity (within about 1 mm) of a reaction chamber wall, where thereaction chamber wall is in thermal contact with a heat exchanger. Heattransfer from the reaction chamber is preferably enhanced by addition ofmicrochannels on at least one reaction chamber wall on the side of tothe reaction chamber wall opposite the catalyst structure. The catalystpreferably has contiguous and relatively large pores, such as in a foam,to avoid large pressure drops. Preferably the pore size of the largepores in the catalyst is between about 10 μm and about 300 μm.

In preferred embodiments of the present invention, carbon monoxidehydrogenation is conducted at a contact time of less than 5 seconds,more preferably, less than about 2 seconds and still more preferablybetween about 0.1 and about 1 seconds. At these contact times, good COconversion and low methane selectivity can be obtained. Preferably, COconversion is at least 25%, more preferably, at least 50%, and stillmore preferably, greater than about 80%. Methane selectivity ispreferably less than 25%, more preferably less than about 20%, and stillmore preferably, between about 15% and 5%. Additionally, theseproperties can be achieved with low pressure drops across the reactionchamber. In the present invention, the pressure drop through thereaction chamber is preferably less than about 15 psig, more preferablyless than 10 psig, still more preferably less than about 5 psig, and yetmore preferably less than about 1 psig.

A method of making the inventive catalyst has the steps of selecting aporous support 100, optionally depositing a buffer layer 102 on theporous support 100 and depositing an interfacial layer 104 thereover.Optionally a catalyst layer 106 may be deposited onto the interfaciallayer 104. or both the interfacial layer and the catalyst layer may besimultaneously deposited on the buffer layer 102.

Because metal has web surfaces that are nonporous and smooth, depositionof a buffer layer or interfacial layer may be impeded. One way tomitigate this problem is to rough the metal surface via chemicaletching. The adhesion of high surface area supported metal catalysts,such as gamma-alumina, to metal foam is significantly improved whenmetal foam is roughed via chemical etching using mineral acid solutions,for example 0.1 to 1M HCl. Roughed web surface also shows improvedresistance to the spalling of catalyst layer under thermal cyclings. Ina preferred embodiment, wherein a metal foam is used as the poroussupport 100, the metal foam is etched prior to vapor depositing thebuffer layer 102. Etching is preferably with an acid, for example HCl.

Deposition of the buffer layer 102 is preferably by vapor depositionincluding but not limited to chemical vapor deposition, physical vapordeposition or combinations thereof. Surprisingly, it has been found thatvapor deposition, which is typically conducted at high temperatures,results in polycrystalline or amorphous phases that provide goodadhesion of the buffer layer to the surface of the porous support. Themethod is particularly advantageous for adhering a metal oxide bufferlayer to a metal porous support. Alternatively, the buffer layer 102 maybe obtained by solution coating. For example, the solution coating hasthe steps of metal surface functionalization via exposing the metalsurface to water vapor to form suface hydroxyls, followed by surfacereaction and hydrolysis of alkoxides to obtain a coating of metal oxide.This solution coating may be preferred as a lower cost method ofdepositing the buffer layer 102.

The interfacial layer 104 is preferably formed by vapor or solutiondeposition using precursors as are known for these techniques. Suitableprecursors include organometallic compounds, halides, carbonyls,acetonates, acetates, metals, colloidal dispersions of metal oxides,nitrates, slurries, etc. For example, a porous alumina interfacial layercan be wash-coated with PQ alumina (Nyacol Products, Ashland, Mass.)colloidal dispersion followed by drying in a vacuum oven overnight andcalcining at 500° C. for 2 hours.

The catalytically active material can be deposited by any suitablemethod. For example, catalytic metal precursors can be deposited oncolloidal metal oxide particles and slurry coated on a porous support,then dried and reduced.

Example 1

The effect of residence time and reaction temperature on the catalyticconversion of CO with H₂ was examined in a constant flow reactor. Thereactor was supplied with a mixture of feed gas, comprised of H₂ and COin a molar, or volumetric (assuming ideal gas behavior), ratio ofH₂/CO=3. This reactant feed was fed into a reaction chamber, which wasmaintained at a constant temperature inside an isothermal furnace. Theinterior of the catalyst chamber measures 35.6-mm (1.4-in) in length,1.5-mm (0.060-in) in thickness and 8-mm (0.315-in) in width. Thereaction products then exited the reaction chamber and were collectedand analyzed for composition.

The catalyst for this experiment was prepared as follows. First, acidicgamma-alumina support powder (Strem) was ground and sieved to between70- and 100-mesh (150 to 220-micron), and calcined (stabilized) at 500°C. for several hours. This powder was then impregnated with a solutioncontaining cobalt nitrate hexahydrate and ruthenium trichloride hydrate(or ruthenium nitrosyl nitrate) precursors, present in desiredconcentrations as to produce a 15-wt % cobalt, 1-wt % ruthenium onalumina catalyst. The precursor solution was prepared in such a manneras to saturate the pore volume of the alumina support without oversaturation of the alumina support. This powder was then dried in avacuum oven at 100° C. for at least 4-hours, followed by drying at 100°C. for at least 12-hours. The powder was then calcined by heating at350° C. for at least 3-hours. A portion of the powder was then combinedwith distilled water in a water-to-catalyst weight ratio of at least 2.5to produce a catalyst slurry. This catalyst slurry is then placed in acontainer with inert grinding media balls and placed on a rotatingdevice for at least 24-hours. This slurry was then ready to coat apre-treated metal foam monolith type support. The metal foam supportmonolith is typically 80-ppi (pores per inch) stainless steel (suppliedby AstroMet, Cincinnati, Ohio), with characteristic macropores on theorder of about 200- to 250-μm, and with a porosity of about 90% (byvolume). The monolith pretreatment consists of cleaning successively indichloromethane and acetone solvents in a water bath submersed in asonication device to agitate the solvent within the monolith.Optionally, the metal surface of the monolith may then be roughened byetching with acid. If this is desired, the monolith is submerged in0.1-molar nitric acid, and placed in a sonication device. The monolithwas then rinsed in distilled water and dried at about 100° C. Themonolith was then coated with a layer of alumina using a chemical vapordeposition (CVD) technique. The CVD system has a horizontal, hot-wallreactor with three precursor sources. The CVD coatings are performed ata deposition temperature of 600° C. and reactor pressure of 5-torr.Aluminum iso-propoxide was used as the aluminum precursor. Thisprecursor is stored in a quartz container maintained at 100° C. duringdeposition, which produces a vapor that is carried into the CVD reactorby a flow of nitrogen carrier gas for about 20-minutes. Air was thenused to oxidize the aluminum precursor to alumina. Typical thickness ofthe alumina coatings is about 0.5-μm. This pretreated metal support foammonolith was then coated with the catalyst slurry by dip coating. Themonolith was then dried in flowing air or nitrogen at room temperaturewhile continuously rotating the monolith in such a way as to create auniform coverage of the dried catalyst slurry layer. The monolith wasthen dried at 90° C. for at least 1-hour, heated slowly to 120° C. overthe course of at least-hour, dried further at 120° C. for at least2-hours, and then heated to 350° C. and calcined for at least 3-hours.Typically, 0.1-0.25 g of alumina supported Co—Ru powder catalyst wascoated on the metal foam monolith with dimensions and characteristicsaforementioned.

The catalyst monolith or powder, weighing approximately 0.5 grams wasthen placed inside the reaction chamber and activated (or reduced) priorto reaction by heating to about 350° C. to 400° C. and under flow of ahydrogen-containing stream of about 10- to 20-% (by mole or volume)hydrogen in an inert carrier gas (such as nitrogen or helium) at a flowrate of at least 20 cc/min (measured at 273K and 1-atm) for at least2-hours. The catalyst was then allowed to cool to reaction temperatures,at least 200° C. The catalyst was then exposed to a feed gas comprisedof H₂ and CO in a desired ratio of moles of H₂ per mole of CO. The feedgas flow rate is controllable to allow for precise generation of adesired contact time, usually about 1-second. The reaction products werethen analyzed to evaluate the conversion of CO and the selectivitytowards certain products, such as methane. The reaction was conducted atpressures up to 24-atmospheres (about 353-psia).

Table E1-1 shows the results of these experiments. In general, thepowder form of the catalyst produced greater conversions at a giventemperature than the monolithic form. However, at a given temperature,the monolith catalyst produced less methane. In conventionalFischer-Tropsch reactors, methane formation is predominately affected byreactor temperature and feed composition, although it is also affectedto a lesser extent by other parameters, such as contact time. The factthat the monolithic catalyst yields lower methane selectivity at a giventemperature suggests that the monolith is better able to conduct heataway from the inner part of the reactor, and thus avoid higher localtemperatures, which are often present in the inner sections of packed orpowder beds. For the monolithic catalyst, conversion is a strongfunction of both temperature and contact time, and conversion willincrease with increasing temperature and/or time. Decreasing the contacttime from 2-seconds to 1-sec at 275° C. for the monolithic catalystsresulted in lower conversion and higher methane selectivity.

When compared to the results of previous studies in Table 1, severalcharacteristics are apparent:

compared to all of these references, sufficient catalyst performance(conversion greater than about 50% and methane selectivity below about25%) can be achieved at a contact time that is about three- totwelve-times shorter

formation of methane, which is highly favored at high reactortemperatures and the hydrogen-to-carbon feed ratios, is intermediate toreferences 1 and 3, which utilize the most similar contact times;however, the monolithic catalyst produces comparable methaneselectivities under conditions which are much more unfavorable than usedin these references. The monolith form was able to produce this amountof methane at temperatures up to 260° C. (compared to 240° C. inreference 1) and a H₂-to CO feed ratio of 3 (compared to 2 forreferences 1 and 3). This further shows that the monolithic form removesheat more effectively that powder or pellet forms, and that methaneformation can be suppressed, even under undesirable conditions.

at a comparable H₂-to-CO feed ratio of 3 and CO conversion (about 80%),the powdered catalyst in reference 7 produces much higher selectivity tomethane than the inventive catalyst even at lower temperatures andlonger contact times, where methane formation is unfavored. Note that inreference 7, a change in H₂-to-CO feed ratio of from 2 to 3 nearlytripled methane selectivity.

In addition, the thickness of the catalyst layer in the monolith(typically less than 20-μm) is much less than finest particle size usedeither in fixed bed reactors (>100 μm), or slurry type or fluidized typereactors (>50-μm). Therefore, the internal mass transfer diffusionpathway is shorter in the monolith catalyst. Moreover, underFischer-Tropsch synthesis operations, internal pores within the catalystare normally filled with hydrocarbon products, and hydrogen has muchhigher diffusivities than that of CO. This could result in much higherH₂/CO ratio inside a pellet or powder catalyst than that in the bulkfeed, which favors methanation. Therefore, the thinner catalyst layerwith the monolith catalyst will result in a relatively lower local H₂concentration within the catalyst to minimize the selectivity tomethane. Yet another advantage of porous catalysts is their efficientuse of space in which molecules can pass through and react inside thecatalyst, without causing excessive pressure drops.

TABLE E1-1 Fischer-Tropsch Catalyst Performance Contact CH₄ CatalystConditions time Convrsion selectivity Co—Ru/Al₂O₃/ 231° C., 24-atm,1-sec 17% 9.6%  foam H₂/CO = 3 Co—Ru/Al₂O₃/ 247° C., 24-atm, 1-sec 29%15% foam H₂/CO = 3 Co—Ru/Al₂O₃/ 264° C., 24-atm, 1-sec 50% 22% foamH₂/CO = 3 Co—Ru/Al₂O₃/ 264° C., 24-atm, 1-sec 49% 22% foam H₂/CO = 3Co—Ru/Al₂O₃/ 275° C., 24-atm, 1-sec 69% 24% foam H₂/CO = 3 Co—Ru/Al₂O₃/275° C., 24-atm, 2-sec 84% 9.0%  foam H₂/CO = 3 Co—Ru/Al₂O₃/ 245° C., 24atm, 1-sec 33% 12% foam H₂/CO = 3 Co—Ru/Al₂O₃/ 245° C., 24 atm, 1-sec99.6%  36% powder H₂/CO = 3

Example 2

An experiment was conducted to demonstrate operation at variouspressures. The equipment was the same as in Example 1.

According to the literature, variation in pressure should only affecttrue residence time in Fischer-Tropsch synthesis. In other words,conventional wisdom in Fischer-Tropsch reactions is that reaction rateis proportional to pressure under identical residence time. However, asshown in Table E2-1, with the catalyst structure of the presentinvention, catalyst activity was unexpectedly enhanced as the pressurewas decreased under the same residence time. This surprising result isattributed to the enhanced mass and heat transfer possible with thecatalyst structure of the present invention.

TABLE E2-1 Engineered catalyst performance for Fischer-Tropsch synthesisat about 250° C. under a constant residence time (i.e., temperature andpressure corrected contact time) of 12.5 seconds. The contact time at 24atm (absolute) is 1 sec. Pressure, atm Selectivity (absolute)Conversion, % to CH₄, % 6 63 18 7 41 22 11 34 19 24 24 26

Example 3

Use of acidic gamma alumina supported Co or Ru alone as a catalyst on tothe metal foam was also tested under the conditions of Example 1 andperformance was found to be worse than that of bimetallic catalyst suchas Co—Ru.

Example 4

An experiment was conducted to demonstrate certain advantages of thebuffer layer of the present invention.

An unetched stainless steel foam (Astromet, Cincinnati Ohio) was coatedwith 1000 Angstroms TiO₂ via chemical vapor deposition. Titaniumisopropoxide (Strem Chemical, Newburyport, Mass.) was vapor deposited ata temperature ranging from 250 to 800° C. at a pressure of 0.1 to 100torr. Titania coatings with excellent adhesion to the foam were obtainedat a deposition temperature of 600° C. and a reactor pressure of 3 torr.

SEM (scanning electron microscope) analysis showed that the stainlesssteel foam supported gamma-alumina with a TiO₂ buffer layer did not showspalling after several (3) thermal cycles from room temperature to 600°C. In a control experiment with a stainless steel foam support coatedwith gamma-alumina without the TiO₂ buffer layer, severe flaking orspalling of the gamma alumina under the identical testing conditions wasobserved. The uncoated steel foam rapidly oxidized when heated to 500°C. in air (as shown by the weight gain, i.e., thermal gravity, values)while the titania coated steel oxidized relatively slowly. Similarly,uncoated nickel foam oxidized, while, under the same conditions (heatingto 500° C. or 750° C. in air), the titania coated nickel foam showedzero (i.e., undetectable levels of) oxidation.

CLOSURE

While a preferred embodiment of the present invention has been shown anddescribed, it will be apparent to those skilled in the art that manychanges and modifications may be made without departing from theinvention in its broader aspects. The appended claims are thereforeintended to cover all such changes and modifications as fall within thetrue spirit and scope of the invention.

1-12. (canceled)
 13. A catalyst monolithic insert, comprising: a porousmetal support; an interfacial layer disposed over the porous metalsupport; wherein the interfacial layer comprises a nitride, carbide,sulfide, metal oxide, or combinations thereof; wherein the monolithicinsert has a width of 0.1 mm to 2.0 cm, and a thickness of 1.0 cm orless.
 14. A catalyst monolithic insert, comprising: a porous metalsupport having an average pore size of 1 um to 1000 um; an interfaciallayer disposed over the porous metal support; wherein the interfaciallayer comprises a nitride, carbide, sulfide, metal oxide, orcombinations thereof; wherein the monolithic insert has a thickness of1.0 cm or less.